Method for concentrating, removing, and separating selected ions from source solutions using particulate solid supports functionalized with polyhydroxypyridinone ligands

ABSTRACT

Compositions and methods for selectively binding metal ions from a source solution comprise using a polyhydroxypyridinone-containing ligand covalently bonded to a particulate solid support through a hydrophilic spacer of the formula SS-A-X-L (HOPO) n  where SS is a particulate solid support such as silica or a polymeric bead, A is a covalent linkage mechanism, X is a hydrophilic spacer grouping, L is a ligand carrier, HOPO is a hydroxypyridinone appropriately spaced on the ligand carrier to provide a minimum of six functional coordination metal binding sites, and n is an integer of 3 to 6 with the proviso that when SS is a particulate organic polymer, A-X may be combined as a single covalent linkage. The separation is accomplished by passing a source solution containing the ions to be separated through a column containing the particulate composition, causing the selected ions to be complexed to the HOPO ligands and subsequently removing the selected ions from the column by passing an aqueous receiving solution through the column and quantitatively stripping the selected ions from the HOPO ligand.

This is a division of application Ser. No. 09/330,477 filed Jun. 11,1999, now U.S. Pat. No. 6,232,265.

BACKGROUND OF THE INVENTION

Effective methods for the recovery and/or separation of particular ionssuch-as the transition, post-transition, lanthanide and radioactiveactinide metal ions from solution mixtures of these and other metalions, are of great importance in modern technology. It is particularlydifficult to remove these particular metal ions in the presence ofmoderate to strong acids and soluble complexing or chelating agents,such as the halide ions, which have a high affinity for the desiredmetal ions. It is also difficult to remove the mentioned desired metalions when they are present at low concentrations in solutions containingother metal ions at much greater concentrations. Hence, there is a realneed for a process to selectively concentrate certain transition,post-transition, lanthanide and actinide metal ions when present at lowconcentrations and in the presence of acid solutions and othercomplexing agents.

It is known that siderophores (compounds manufactured by microorganismsto sequester Fe³⁻ ions) are commonly composed of hydroxamate- andcatecholate-containing molecules. Formulas 1 and 2 show thesestructures.

A modern review of the siderophores is found in an article by J. R.Telford and K. N. Raymond, “Comprehensive Supramolecular Chemistry,”vol. 10, Ed. by D. N. Reinhoudt, Pergamon Press, 1996, pp. 245-266. Manysynthetic iron chelating agents have been prepared in an effort to findpharmaceutical compounds that will increase the excretion of iron fromiron-overloaded patients. Some of the synthetic chelating agents containthe hydroxypyridinone structure as depicted by3-hydroxy-2(1H)-pyridinone (Formula 3), 1-hydroxy-2(1H)-pyridinone(Formula 4), and 3-hydroxy-4(1H)-pyridinone (Formula 5).

These chelating agents often have other substituents, such as carboxylgroups in positions 3, 4, 5, or 6 of the compound in Formula 4 or alkyland carboxymethyl groups on the nitrogen atoms of the compounds inFormulas 3 and 5. These hydroxypyridinone structures are excellentcomplexing agents for Fe³⁺ because the pyridone carbonyl oxygen atomswithdraw electron density and have a partial negative charge as shown inthe resonance structures for 1-hydroxy-2(1H)-pyridinone below.

Thus, these materials resemble the hydroxamate molecules that have ahigh affinity for Fe³⁺. The synthesis and Fe³⁺ ion-complexing propertiesof these types of compounds are found in the article by K. N. Raymondand his coworkers, “Ferric Ion Sequestering Agents. 13. Synthesis,Structures, And Thermodynamics of Complexation of Cobalt(III) AndIron(III) Tris Complexes of Several Chelating Hydroxypyridinones,”Inorganic Chemistry, Volume 24, 1985, pp. 954-967; and in the article byP. D. Taylor and his Coworkers, “Novel 3-hydroxy-2(1H)-pyridinones.Synthesis, Iron(III)-chelating Properties And Biological Activity,”Journal of Medicinal Chemistry, Volume 33, 1990, pp. 1749-1755. K. N.Raymond and his coworkers have found that having more than one of thesechelating groups bonded to a polyamine such as1,5,10,14-tetraazatetradecane improves their affinity for Fe³⁺ andallows complex formation with the actinides. Bonding to the polyamine isthrough the formation of amide bonds as shown in following Formula 6.

The octadenate ligand shown above in Formula 6 has a high affinity forFe(III), Am(III), Pu(IV) and Np(V) as reported in articles by K. N.Raymond and coworkers, “Specific Sequestering Agents For The Actinides.21. Synthesis And Initial Biological Testing of Octadentate MixedCatecholate-hydroxypyridinoate Ligands,” Journal of Medicinal Chemistry,Volume 36, 1993, pp. 504-509; and “In Vivo Chelation of Am(III), Pu(IV),Np(V) Ad U(VI) in Mice by Tren-(Me-3,2-HOPO),” Radiation ProtectionDosimetry, Volume 53, pp. 305-309. A similar polyamine materialcontaining three Formula 3 HOPO molecules formed strong interactionswith gadolinium, calcium and zinc as shown in the article by J. Xu, S.J. Franklin, D. W. Whisenhunt, Jr., and K. N. Raymond, “GadoliniumComplex ofTris[(3-hydroxy-1-methyl-2-oxo-1,2-didehydropyridine-4-carboxamido)ethyl]amine:A New Class of Gadolinium Magnetic Resonance Relaxation Agents,” Journalof the American Chemical Society, Volume 117, 1995, pp. 7245-7246. Thesynthesis of hydroxypyridinonate chelating agents, such as that shownabove in Formula 6, is shown by Raymond et al., U.S. Pat. No. 4,698,431,issued Oct. 6, 1987. The materials described in this patent and theabove cited articles are directed only to the hydroxypyridonatemolecules or those bound to simple amines. Attachment of from one tofour HOPO rings to a molecular or polymeric backbone through amidelinkages is taught by Raymond et al., U.S. Pat. No. 5,624,901, issuedApr. 29, 1997. At least one of the HOPO rings must be a 3,2-HOPO ligand.Tetra-, hexa- and octadentate ligands (i.e. two to four HOPOsubstituents) are illustrated being attached to a polyamine linkingbackbone. There is also an allegation that a polymeric backbone, such aspoly(styrenedivinylbenzene), agarose and polyacrylamide, having aminefunctionalities, can be used to which a HOPO substituent can be directlybonded via an amide-type linkage. There is no teaching or suggestionthat a tetra-, hexa- or octadentate HOPO ligands, attached to a backbonecarrier, can be covalently attached to a polymeric or inorganic solidsupport through the backbone carrier by appropriate linkage means.

The ability to complex Fe³⁺, Pu⁴⁺, Th⁴⁺, Zr⁴⁻, lanthanides, actinidesand other metal ions under increasing acidities and competing matrixcomplexers or chelants requires the interactive strength of six to eightdonor atoms, of which there are two per HOPO ring, and the propermolecular spacing of these HOPO rings. The ability to use thisinteractive strength to perform an actual separation requires that threeor more HOPO moieties with appropriate molecular spacing be attached viaa stable covalent bond to a solid support in such a manner that the HOPOmoieties cooperate in such a manner to maximize their collective bindingabilities.

SUMMARY OF THE INVENTION

The present invention provides a composition and method for the removalof desired transition, post-transition, actinide and lanthanide metalions present in low concentrations from a solution utilizingcompositions comprising three or more hydroxylpyridinonate (HOPO)containing ligands the composite of which are appropriately spaced so asto contain the interactive strength of six or more coordination bindingsites, preferably six to eight. The HOPO containing ligands arecovalently bonded to a particulate solid support via an appropriatehydrophilic hydrocarbon spacer.

This invention also provides a composition and method of maximizing thecomplexing abilities of ligands containing three or more HOPO bindingmoieties by the preparation of ligands wherein the HOPO moieties areproperly spaced on a ligand carrier and the ligand is attached to aninorganic or organic particulate solid support via an appropriatehydrophilic hydrocarbon spacer.

The compositions of the present invention comprise suitable ligandscontaining three or more HOPO groups, such as the HOPO groups notedabove, which are covalently bonded through a hydrophilic spacer groupingto a silicon, carbon, nitrogen, oxygen or sulfur atom and furthercovalently bonded to a particulate inorganic or polymeric organic solidsupport and are represented by the following Formula 7:

SS-A-X-L(HOPO)_(n)  Formula 7

wherein SS is a solid support, A is a covalent linkage mechanism, X is ahydrophilic spacer grouping, and L(HOPO)_(n) is a ligand comprising aligand carrier L having bound thereto three or more HOPO groups, whereinthe ligand carrier L is configured such that the HOPO groups areappropriately spaced on the ligand carrier to provide six or morefunctional coordination binding sites.

In the above Formula 7, n is an integer of at least three and may rangefrom about 3 to 6. Preferably n is an integer of 3 or 4. Preferably, theHOPO groups are positioned on carrier L such that there are at least twoand preferably at least four atoms on carrier L separating the attachedHOPO groups to provide the appropriate stereoconfiguration to optimizethe HOPO binding sites. When considering the atoms separating the HOPOgroups, the hydrogen atom is not taken into consideration. When theligand carrier L is non-cyclic the HOPO groups on the carrier willpreferably be spaced apart by 4 to 6 atoms and when the ligand carrieris an amine the HOPO groups will separated by four or more non-hydrogenatoms. Preferably the carrier is a polyamine wherein an aminefunctionality on the ligand carrier interacts with an active functionalgroup on the hydroxypyridinone to form a covalent bond. Representativeligand carriers illustrated in the examples below include membersselected from the group consisting of tetrakis(aminomethyl)methane;tetrakis(5-amino-2-oxa-pentyl)methane;25,26,27,28-tetrakis[(aminobutyl)oxy]calix[4]arene;1,4,8,12-tetrazacyclopendadecane and triethylenetetraamine. The aboveligand carriers are exemplary only and any carrier to which a HOPOmoiety can be appropriately spaced and bonded, such that the metalcoordination sites of the HOPO moiety can be utilized in ion binding,are within the scope of the invention.

Functional hydroxypyridinone structures are shown in Formulas 3, 4 and 5and, regardless of their positions on the pyridinone ring, alwayscomprise adjacent hydroxy and oxo groupings. This provides the HOPOgroup with a sequestering functionality similar to the siderophoresshown in Formulas 1 and 2. Formula 3 shows a 3-hydroxy-2(1H)-pyridinone,Formula 4 shows a 1-hydroxy-2(1H)-pyridinone and Formula 5 shows a3-hydroxy-4(1H)-pyridinone. In addition to the hydroxy and oxofunctions, at least one other ring atom contains a functional groupingthrough which a covalent bond can be formed to attach the HOPO group tothe ligand carrier to provide the overall multi HOPO containing ligand.Preferably, when attached to a carbon atom of the HOPO ring, thefunctional group will be a carboxylic acid group that will react throughamidation or esterification with an amino or hydroxy group of the ligandcarrier. When the functional group is attached to the nitrogen atom ofthe pyridinone ring it will preferably be an alkyl or carboxyalkylgroup. Carboxylic acid functional groups that react with an aminefunction on the ligand carrier forming an amide bond are particularlypreferred.

In order for the HOPO groups of the —L(HOPO)_(n) portion of Formula 7 tofunction with optimal binding selectivity, it is important that thestereoconfiguration of the HOPO moieties be such that the coordinationsites of each HOPO ring can function optimally for the binding andremoval of the desired ions. At the same time, it is vital that the—L(HOPO)_(n) functionality be firmly anchored to a solid support suchthat desired ions removed from solutions can be complexed to the bindingligands and then, optionally, subsequently released in such a mannerthat the binding/release process can be repeatedly utilized as desired.This is accomplished by means of a SS-A-X- portion of Formula 7.

The SS-A-X- portion of Formula 7 is well known for use with ion bindingligands. Preferably solid support “SS” is an inorganic and/or organicparticulate support material selected from the group consisting ofsilica, silica gel, silicates, zirconia, titania, alumina, nickel oxide,glass beads, phenolic resins, polystyrenes and polyacrylates. However,other organic resins or any other hydrophilic organic and/or inorganicsupport materials meeting the above criteria can also be used.

The use of organic ion binding ligands attached to an SS-A-X- solidsupport by means of a covalent linkage spacer grouping is illustrated inU.S. Pat. Nos. 4,943,375; 4,952,321; 4,959,153; 4,960,882; 5,039,419;5,071,819; 5,078,978; 5,084,430; 5,173,470; 5,179,213; 5,182,251;5,190,661; 5,244,856; 5,273,660; and 5,393,892. These patents, whichdisclose various spacers that can be used in forming an organic ligandattached to a solid support, are incorporated herein by reference.

When the solid support SS is an inorganic material such as silica,silica gel, silicates, zirconia, titania, alumina, nickel oxide andglass beads the covalent linkage A is a silane such that A-X may berepresented by the formula:

where X is a spacer grouping having the formula:

(CH₂)_(a)(OCH₂CHR¹CH₂)_(b)  Formula 9

wherein R¹ is a member selected from the group consisting of H, SH, OH,lower alkyl, and aryl; a is an integer from 3 to about 10; and b is aninteger of 0 or 1. Each Z is independently selected from the groupconsisting of Cl, Br, I, lower alkyl, lower alkoxy, substituted loweralkyl or substituted lower alkoxy and S. As used herein, lower alkyl orlower alkoxy means a group having 1 to 8 carbon atoms.

When the particulate solid support (SS) is an organic resin or polymer,such as phenolic resins, polystyrenes and polyacrylates, it willgenerally be a hydrophilic polymer or polymer derivatized to have ahydrophilic surface and contain polar functional groups. The ligandL(HOPO)_(n) will then generally contain a functional grouping reactivewith an activated polar group on the polymer. The covalent linkage A andspacer X will then be integrated, and may actually be a single linkage,formed by the covalent bonding formed by the reaction between theactivated polar group from the polymer and the functional group from theligand and may be represented by formula:

—(CH₂)_(x)—(Y)_(y)—(CH₂)_(z)—  Formula 10

where c is an integer of 0 or 1, d and e are independently integersbetween 0 and 10 and Y is a functional group or aromatic linkage such asan ether(O), sulfide(S), imine(C═N), carbonyl(CO), ester(COO),thioester(CSO), amide(CONH), thioamide(CSNH), amine(NH), loweralkylamine(NR), sulfoxide(SO), sulfone(SO₂), sulfonamide (SO₂NH), phenyl(C₆H₄), benzyl(CH₂C₆h₄), and the like. At least one of x, y or z must be1.

It is to be emphasized that the present invention does not reside in thediscovery of the SS-A-X- portion of Formula 7. Rather, it is thediscovery that the ion-binding capabilities of the L(HOPO)_(n) ligand,when attached to an SS-A-X based solid substrates, are optimized.

The properly spaced polyhydroxypyridinone ligands covalently bonded tosolid supports as shown in Formula 7 are characterized by highselectivity for and removal and separation of desired metal ions orgroups of desired metal ions, such as several transition,post-transition, lanthanide and actinide metal ions, includingparticularly Fe³⁺, Al³⁺, Zr⁴⁺, Th⁴⁺, Pu⁴⁺, AM³⁺, Cm³⁺, Ac³⁺, and thelanthanides present at low concentrations from source solutionscontaining a mixture of these desired metal ions with the ions one doesnot desire to remove which may be present in much greater concentrationsin the source solution including hydrogen ions. The separation iseffected in a separation device such as a column through which thesource solution is flowed. The process of selectively removing andconcentrating the desired metal ions is characterized by the ability toselectively and quantitatively complex the desired metal ions to theproperly spaced polyhydroxypyridinone ligand portion of the solidsupport system, from a large volume of solution, even though the desiredmetal ions may be present at low concentrations. The desired ions thusseparated can, optionally, be subsequently recovered from the separationcolumn by flowing through it a small volume of a receiving phase whichcontains a solubilized reagent which need not be selective, but whichwill quantitatively dissociate the desired ions from thehydroxypyridinone ligands. The recovery of the desired metal ions fromthe receiving phase is easily accomplished by known procedures.

Moreover, the above described ligands covalently bonded to particulatesolid supports as shown in Formula 7 provide a means for separatingparts-per-billion (ppb) to parts-per-million (ppm) levels of Fe³⁻ from1% to 5% HF or NH₄F by using the separation techniques described above.The solid supported ligands of this invention are also useful inseparating Pu(IV), Th(IV), Zr(IV), and Hf(IV) from >1M nitric acidsolutions and in separating other acid solutions of actinides andlanthanides containing large amounts of other cations. The abovedescribed solid supported ligands are also effective in separating Cu,Ni, Zn, Cd, Pb, Ag, Hg and others as wastes from less acidic feedstreams such as potable water or industrial effluents.

DETAILED DESCRIPTION OF THE INVENTION

As summarized above, the present invention is drawn to novel properlyspaced polyhydroxypyridinone-containing ligands covalently bound toparticulate solid support materials to form the compositions of Formula7. The invention is also drawn to the concentration and removal ofcertain desired metal ions, such as certain transition, post-transition,lanthanide and actinide metal ions, from other metal ions in watersupplies and waste solutions, such as ions of Fe, Pu, Th, Zr, Hf, otherlanthanides and actinides, Bi, and Sb from acidic and/or highlycomplexing or chelating matrices and Cu, Al, Ga, Ni, Zn, Cd, Pb, Ag, andHg ions from slightly acidic to neutral pH matrices and other chelatingmatrices. Moreover, the above described ligands covalently bonded toparticulate solid supports as shown in Formula 7 provide a means forseparating ppb to ppm levels of Fe from concentrated 1% to 5% HF andNH₄F by using the separation techniques described above. The process ofthe invention is particularly adaptable to recovery of metal ions fromsolutions containing large amounts of hydrogen ions and other ligatinganions such as fluoride. Such solutions from which such ions are to beconcentrated and/or recovered are referred to herein as “sourcesolutions.” In many instances the concentration of desired ions in thesource solutions will be much less than the concentration of other metalions from which they are to be separated.

The concentration of desired ions is accomplished by forming a complexof the desired ions with a polyhydroxypyridinone-containing ligandparticulate solid support composition shown in Formula 7 and flowing asource solution containing the desired ions through a column packed witha polyhydroxypyridinone ligand-solid support composition to attract andbind the desired metal ions to the polyhydroxypyridinone ligand portionof such composition to form a ligand-metal ion complex, and subsequentlydissociating the ligand-metal ion complex by flowing a receiving liquidin much smaller volume than the volume of source solution passed throughthe column to remove and concentrate the desired ions in the receivingliquid solution. The receiving liquid or recovery solution forms astronger complex with the desired transition, post-transition lanthanideor actinide metal ions than does the polyhydroxypyridinone ligand andthus the desired metal ions are quantitatively stripped from thehydroxypyridinone ligand-containing solid support composition inconcentrated form in the receiving solution. The recovery of desiredmetal ions from the receiving liquid can be accomplished by knownmethods.

EXAMPLES

The following examples illustrate the preferred embodiments of theinvention that are presently best known. However, other embodiments maybe made within the scope of the disclosure. In certain of she examples,reaction schemes are given that are general in nature and reference tothe text of each example may be necessary to clarify each reactant,reaction step, reaction condition and product obtained. Reactantsutilized and/or products prepared are identified by the number of theexample followed by an alphabetical designation in which each was firstused, i.e. “1A” is the first reactant or product identified in Example1, “1B” is the second, etc. All NMR spectra were obtained on QE 300 (300MHZ) spectrophotometer.

Example 1 Preparation of 1-hydroxy-2-(IH)-pyridinone-6-carboxylic Acid(1C)

The starting material used for this reaction can be either 6-chloro or6-bromo-pyridine-2-carboxylic acid. The chloro derivative is preferredand is illustrated here. A 643 g (4.08 mole) portion of6-chloro-pyridine-2-carboxylic acid (1A) was added to a solution of 10.6L of CF₃COOH and 1530 mL of 30% H₂O₂ and heated to 80° C. for 6.5 hrs.The reaction mixture was concentrated to about 2100 mL by rotaryevaporation and then added to 1 L of water. The product immediatelyprecipitated as a finely divided, white crystalline solid. It wasisolated by filtration, washed with water, and dried in vacuo. Thisyielded 687 g of 2-chloropyridine-2-carboxylic acid (1B), mp 180° C.dec. ¹HNMR (DMSO-d₆): S 8.20 (m,2H), 7.80 (m,1H), −2.70 (broad S, 1H)

A 687 g (3.96 mole) portion of the 2-chloro-pyridine-6-carboxylic acid(1B) prepared above was dissolved in 15 L of a 10% aqueous KOH solution,and the resulting solution was maintained at 80° C. overnight and thencooled in an ice bath and treated with 7.2 L of concentrated HCl. Thewhite suspended solid was isolated by filtration, washed with dilute HClfollowed by three 1.3 liter portions of water, and then dried in vacuoto yield 530 g (86%) of 1-hydroxy-2-(IH)-pyridinone-6-carboxylic acid(1C). mp 216° C. dec. ¹HNMR (DMSO-d6): S 13.02 (broad s, 2H), 7.44 (m,1H), 6.73 (d, J=9.5 Hz, 1H), 6.65 (d, J=7.5 Hz, 1H).

Examples 2-4 illustrate the preparation of ligand carriers.

Example 2 Preparation of Tetrakis(aminomethyl)methane (TAM) (2C)

A 250-mL three-necked reaction flask, equipped with a mechanical stirrerand a thermometer, was heated in an oil bath to 210° C. Pentaery-thrityltetrabromide (2A) was ground well with the sodium salt ofp-toluenesulfonamide and added in four (equal) amounts to the preheatedreaction vessel while stirring. The reaction mixture formed a viscousmelt within 40 minutes (oil bath 230° C. by electro-thermometer). Themelt was maintained under stirring at 210° C. for 8 hrs. Pentaerythrityltetrabromide sublimity on the cooler parts of the reaction flask wasmelted down occasionally by pumping hot oil from the oil bath. Thereaction mixture was cooled to 180° C. under stirring and then allowedto cool to room temperature. Acetic acid (70% v/v, 60 mL) was added tothe reaction flask equipped with a reflux condenser and the contentsrefluxed until the hard reaction mixture disintegrated into a fine whitesuspension. The mixture was washed several times with hot water toremove sodium bromide and p-toluenesulfonamide. The resulting whitecrystalline powder weighed 50 g (62%) and was found to be puretetratosylate of TAM (2B). mp 248° C. ¹HNMR (CHCl₃): S 7.70 (d, J=9.0Hz, 8H), S 7.33 (d, J=9.0 Hz, 8H), 5.40 (t, J=6.7 Hz, 4H, NH), 2.68 (d,J=6.7 Hz, 8H), 2.44 (S, 12H).

Concentrated sulfuric acid was taken in a three-necked flask equippedwith a mechanical stirrer and heated to 160° C. in an oil bath. Thepowdered tosylate (2B) from above was added in small lots over 40minutes. The tosylate dissolved immediately to form a clear solution andthe temperature rose to 180° C. The reaction mixture was maintained at180° C. for 30 minutes. After cooling to room temperature and pouringinto 30% v/v ethanol, the white crystalline solid formed was allowed tosettle. The supernatant was decanted off and the precipitate wasdissolved in a minimum amount of 10% sodium hydroxide and filtered toremove any insoluble material. The filtrate was evaporated to dryness.The residue was treated with methanol and the solid was filtered off andthe filtrate was evaporated to dryness with the help of toluene. Thepure TAM product (2C) was obtained by distillation at 110° C./0.4 mm Hgin yield of 76% (2.50 g) mp 70° C. ¹H NMR (CDCl₃): S 2.58 (S, 8H) , 1.11(S, 8H, NH₂)

Example 3 Preparation of Tetrakis (5-amino-2-oxa-pentyl)methane (3C)

A mixture of 13.62 g (0.10 mole) of pentaerythritol (3A) and 1 g of a40% Ag/KOH catalyst was stirred while 42.45 g (0.80 mole) ofacrylonitrile was added at a rate such that the temperature did notexceed 35° C. The mixture was stirred an hour after all theacrylonitrile was added and poured into 200 mL of water. The resultingmixture was stirred for one hour, which allowed the excess acrylonitrileto polymerize completely. The polymer was removed by filtration andwashed with chloroform. The chloroform layer was washed with water twotimes more and dried over MgSO₄. The crude tetranitrile product (3B) (30g) was produced by the evaporation of chloroform and directly used forthe next reaction without further purification. ¹HNMR (CDCl₃): S 3.78(t, J=6.0 Hz, 8H), 3.59 (S, 8H), 2.69 (t, J=6.0Hz, 8H).

To a solution of the crude tetranitrile (3B) (30 g, 0.10 mole) in HPLCgrade THF (6.5 L) was added dropwise BH₃ (1M in THF, 1.4 L, 1.4 mole)under nitrogen. The reaction mixture was heated at 70° C. overnight.After being cooled, the solution was carefully quenched by the additionof water, and the mixture was stirred for 30 minutes at roomtemperature. The solvent was then distilled off, and the solid residuewas heated to reflux in 6N HCl (800 mL) for 3 hrs while being cooledwith an ice-water bath, and the acidic solution was basified to pH 13with solid NaOH. The water was evaporated to dryness and the tetramineproduct (3C) was extracted with methanol from the residue. The methanolsolution was evaporated to dryness again and trace water was removed byazeotropic distillation with toluene. The residue was treated withCH₂Cl₂ and filtered. The filtration was dried over K₂IO₃. Afterfiltration, the methylene chloride solution was evaporated to dryness.The pure tetrakis(5-amino-2-oxapentyl)methane (3C) was obtained bydistillation under vacuo at 210° C./0.3 mmHg in a yield of 34% (10.7 g).¹HNMR (CDCl₃): S 3.43 (t, J=6.0 Hz, 8H), 3.35 (S, 8H), 2.76 (t, J=6.6Hz, 8H), 1.67 (m, 8H).

Example 4 Preparation of 25,26,27,28-tetrakis[(aminobutyl)oxy]Calix[4]arene (4D)

Calix[4]arene (4A) (3.56 g, 85 mmol), 4-bromo-butyronitrile (2.60 g,17.6 mmol), and potassium carbonate (1.39 g, 10.1 mmol) was refluxed inCH₃CN (100 mL) for 5 days. The solvent was evaporated and the residuewas taken up in CH₂Cl₂ (400 mL), washed with 1N HCl (100 mL), H₂O (60mL), and brine (60 mL), and dried with MgSO₄. The CH₂Cl₂ was evaporatedand the residue was recrystallized from CHCl₃/MeOH yielding a whitesolid 25,27-bis[(cyanopropyl)oxy]-26,28-dihydroxycalix[4]arene product(4B). Yield: 2.61 g (56%). ¹HNMR (CDCl₃): S 7.80 (S, 2H, CH), 7.20 (d,J=7.2 Hz, 4H), 6.92 (d, J=7.2 Hz, 4H), 6.75 (t, J=7.2 Hz, 2H), 6.66 (t,J=7.2 Hz, 2H), 4.18 (d, J=12.6 Hz, 4H) 4.10 (t, J=6.6 Hz, 4H), 3.42 (d,J=12.6 Hz, 4H), 3.10 (t, J=6.6 Hz, 4H), 2.40 (m, 4H).

NaH (1.13 g, 44.7 mmol) and the above25,27-bis[(cyanopropyl)oxy]-26,28-dihydroxycalix[4]arene (4B) (2.50 g,4.5 mmol) was stirred for 1 hr. at room temperature in DMF (100 mL).4-Bromobutyronitrile (6.63 g, 44.7 mmol) was added and the mixture wasstirred at 75° C. for 20 hrs. The DMF was evaporated and the residue wastaken up with CH₂Cl₂ (200 mLs) and washed with 1N HCl (100 mL×2),saturated NH₄Cl in H₂O (100 mL×3), and saturated NaCl in H₂O (100 mL),and dried with MgSO₄. After filtration, the CH₂Cl₂ was evaporated andthe residue was purified by silica gel column (CH₂Cl₂/MeOH=250/)1 andthen recrystallized from MeOH with a yield of 0.43 g (15%) yield25,26,27,28-tetrakis[(cyanopropyl)oxy]calix[4]arene (4C). ¹HNMR (CDCl₃):6.64 (S, 12H), 4.32 (d, J=12.4 Hz, 4H), 4.05 (t, J=6.5 Hz, 8H), 3.24 (d,J=12.4 Hz, 4H) 2.60 (t, J=6.5 Hz, 8H), 2.20 (m, 8H).

A mixture of the tetranitrile (4C) (0.43 g, 0.02 mmol) and 1M BH₃ in THF(10 mL, 10 mmol) was refluxed overnight. After being cooled, thesolution was carefully quenched by the addition of water, and themixture was stirred for 30 minutes at room temperature. The solvent wasthen distilled off, and the solid residue was heated to 65° C. in conc.HCl (10 mL) and MeOH (10 mL) for 2 hrs. After being cooled with anice-water bath, the acidic solution was basified to pH ˜13 with 2N NaOH.After removal of CH₃OH, the product was extracted with CH₂Cl₂ from theaqueous solution. The CH₂Cl₂ solution was dried with Na₂SO₄. Afterfiltering, the filtrate was evaporated to dryness to yield 0.36 g (82%)of 25,26,27,28-tetrakis[(aminobutyl)oxy]calix[4]arene. ¹H NMR CDCl₃):7.10-6.10 (m, 12H), 4.22 (d, J=12.2 Hz, 4H), 4.06-3.58 (m, 16H),3.32-2.78 (m, 12H), 2.10-1.08 (m, 16H). FAB mass spectrum, tm/e 732(M⁺+Na, 18), 710 (M⁻+H, 46), 661 (M⁺ CH₂CH₂CH₂NH₂+H+Na, 41), 639 (M⁺CH₂CH₂CH₂NH₂+2H, 100).

Examples 5-9 illustrate the preparation of tris(HOPO)amine ligands.

Example 5 Preparation of the Tris-HOPO-Amine Ligands

A solution of 1-hydroxy-2-(1H)-pyridinone-6-carboxylic acid (1C) (1.55g, 10 mmol) from Example 1 in DMAA (50 mL) was stirred for 20 minutes. Asolution of CDI (1.62 g, 10 mmol) in DMAA (50 mL) was added dropwiseinto the above solution. The mixture was stirred for 2 hrs. at roomtemperature. The ligand carrier tetrakis (aminomethyl) methane (2C)(0.38 g, 2.9 mmol) from Example 2 was added. The amidation reaction wasallowed to go at room temperature for three days. The solvent wasevaporated and the residue was dissolved in water (20 mL), then treatedwith THF (200 mL) to precipitate the tris(HOPO)amine ligand (5A) shownabove. The solid was collected and washed with CHCl₃. After drying undervacuum at 50° C., the ligand (5A)1-aminoethyl-2[tris(6-methyleneaminocarboxy-1-hydroxy-2-(1H)pyridinone)]weighed 1.35 g. ¹HNMR (DMSO-d6): 9.50 (broad S, 3H), 7.46-7.26 (m, 3H),6.70-6.50 (m, 6H), 3.52-2.94 (m, 8H), 2.40 (S, 5H).

Example 6

A solution of r-hydroxy-2-(1H)-pyridinone-6-carboxylic acid (1C) (96.64g, 0.62 mol) from Example 1 in DMAA (5.5 L) was stirred for 20 minutesand then a solution of CDI (103 g , 0.623 mol) in DMAA (400 mL) wasadded dropwise over half an hour. The mixture was stirred at roomtemperature for 2 hrs. The ligand carrier, tetrakis(5-amino-2-oxy-pentyl)methane (3C) 65.07 g, 0.178 mol) from Example 3was added and the amidation reaction was allowed to carry out at roomtemperature for three days according to the reaction scheme shown above.The solvent was evaporated under vacuum at 60° C. and the residue wasdissolved in 100 mL of methanol. Ethyl ether was poured into themethanol solution to precipitate the crude tris (HOPO) amine ligandproduct (6A). After being decanted the oily product was treated with amixture of methanol and chloroform (1/1) and the insoluble impurity wasfiltered off. The filtrate was evaporated to dryness to afford 152 g ofthe purified tris(HOPO)amine ligand (6A). ¹HNMR (DMSO-d6): S 9.20 (broadm, 3H), 8.40 (broad S, 3H), 7.34-7.15 (m, 3H), 6.54-6.32 (m, 6H),3.48-3.18 (m, 24H), 2.88 (m, 2H), 1.84-1.58 (m, 8H).

EXAMPLE 7

A solution of 1-hydroxy-2-pyridinone-6-carboxylic acid (1C) (0.29 g,1.78 mmol) from Example 1 in DMAA (30 mL) was stirred for 20 minutes andthen a solution of CDI (0.29 g, 1.78 mmol) in DMAA (30 mL) was addeddropwise. The mixture was stirred at room temperature for 2 hrs. Asolution of the carrier ligand 25, 26, 27,22-tetrakis[(aminobutyl)oxy]calix[4] arene (4D) (0.36 g, 0.51 mmol) fromExample 4 in DMAA (20 mL) was added and the reaction was allowed tocarry out at room temperature for three days as shown in the abovereaction scheme. The solvent was evaporated under vacuum at 60° C. andthe residue was treated with ethyl ether. After being decanted, the oilyresidue was dissolved in CHCl₃. Any insoluble impurity was removed byfiltration and the filtrate was concentrated to dryness to afford 0.62 gof the purified tris(HOPO)amine ligand (7A). ¹HNMR (CDCl₃): S 7.68 (m,3H), 7.32-6.16 (m, 21H), 4.32 (m, 4H), 4.00-3.02 (m, 23H), 2.28 (broadS, 2H), 2.14-1.40 (m, 12H).

EXAMPLE 8

A solution of 1-hydroxy-2-(1H)-pyridinone-6-carboxylic acid (1C) (1.55g, 10 mmol) from Example 1 in DMAA (50 mL) was stirred for 20 min. Thena solution of DCI (1.62 g, 10 mmol) in DMAA (50 mL) was added dropwise.The mixture was stirred at room temperature for 2 hrs. A solid ligandcarrier, 1,4,8,12-tetraazacyclopentadecane, (8A) (0.61 g, 2.9 mmol) wasadded and the amidation reaction was allowed to carry out at roomtemperature for three days as shown in the above reaction scheme. Thetris(HOPO)cyclam ligand (8B), as shown, results from the amidationreaction between the 6 carboxylic acid on the HOPO ring with three ofthe N-H functionalities of the tetraazacyclopendadecane. The solvent wasevaporated under vacuum at 60° C. and the residue was treated withmethanol. The solid was collected and washed with methanol andchloroform. After being dried under vacuum at 50C it afforded 1.96 g oftris(HOPO)cyclam ligand (8B). ¹HNMR (DMSO-16): 7.42-7.04 (m, 3H),6.56-5.98 (m, 6H), 3.8-2.56 (m, 20H), 2.12-1.60 (m, 6H).

EXAMPLE 9

A solution of 1-hydroxy-2-(1H)-pyridinone-6-carboxylic acid (1C) (1.55g, 10 mmol) from Example 1 in DMAA (50 mL) was stirred for 20 minutesand then a solution of CDI (1.62 g, 10 mmol) in DMAA (50 mL) was addeddropwise. The mixture was stirred at room temperature for 2 hrs.Triethylenetetraamine (9A) (0.42 g, 2.86 mmol) was added as the ligandcarrier and the resulting mixture was allowed to stir at roomtemperature for three days as shown in the above reaction scheme. Ligand9B, as shown, results from the amidation reaction between the 6carboxylic acid on the HOPO ring with three of the N-H functionalitiesof the triethylenetetramine. The solvent was evaporated under vacuum at60° C. and the residue was dissolved into a small amount of methanol.The tris(HOPO)tetraamine (9B) was precipitated by adding ethyl etherinto the above methanol solution. After being decanted, the oily productwas dissolved in a mixture of methanol and chloroform (1/1). After beingfiltered, evaporation of solvents give 1.45 g of thetris(HOPO)tetraamine ligand (9B). ¹HNMR (DMSO-d6)=9.60 (S 1H) 7.42-7.19(m, 3H), 6.58-6.25 (m, 6H) 3.74-2.96 (m, 14H), 2.82-2.62 (m, 2H).

Examples 10-12 show the attachment of a HOPO ligand to a solid supportby means of a covalent linkage.

EXAMPLE 10 Attachment of a Tris(HOPO)tetramine Ligand Onto Silica Gel

A mixture of silica gel (10A) (35-60 mesh, 28.2 g) in toluene (110 ml)was refluxed with 3-glycidoxypropyltrimethoxysilane (10B) (13.33 g, 56.4mmol) overnight. The functionalized silica gel (10C) was collected byfiltration and washed with MeOH. After being dried in vacuum at 50° C.overnight it was ready for the ligand attachment.

A mixture of the functionalized silica gel (10C) (1 g) and thetri(HOPO)tetramine ligand (6A) of Example 6 in water was gently stirredat 50° C. for three days. The resulting product (10D) was collected byfiltration and washed with water and MeOH. After being dried at 50° C.in vacuum the composition was ready for analytical testing.

The composition (10D) prepared by this Example corresponds to Formula 7wherein SS is silica gel, A is a silane linkage (Formula 8), X is aglycidoxypropyl spacer (Formula 9 where a is 3, b is 1 and R: is OH) andL(HOPO)₃ is the tris(HOPO)tetramine ligand of Example 6.

Example 11 Attachment of Tris(HOPO)tetramine Onto Polyacrylate Beads

Polyacrylate beads (11A) were activated as follows. The pH of 50 mL ofdouble distilled water was adjusted to between 4.9 and 5.1 with4-morpholine ethane sulfonic acid. One gram of polyacrylate beads (11A)were then added to the above solution. Then 0.35 g of1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (11B)was added. After 5 minutes another 0.35 g portion of EDC was added.After being stirred for 15 minutes at room temperature, the activatedbeads were collected by filtration and were ready for the ligandattachment.

The activated beads were plunged into 0.1M of the tris(HOPO)tetramine ofExample 6 (6A) in 25 mL of water and gently stirred overnight. Theligand loaded beads were collected by filtration and washed with water,then MeOH. After being dried, the ligand containing beads (11C) wereready for analytical testing.

The composition (11C) prepared by this Example corresponds to Formula 7wherein SS is polyacrylate, A and X are represented by the carbonylgroup (Formula 10 where d is 0, c is 1, e is 0 and Y is carbonyl)covalently bonding SS to the L(HOPO)³ ligand which is thetris(HOPO)tetramine ligand of Example 6.

Example 12 Attachment of Tris(HOPO)tetramine Onto Polystyrene Beads

A mixture of activated polystyrene beads (1.0 g, 2 mmol Cl) andtris(HOPO)tetramine (6A) (1.55 g, 2 mmol) in water (7 ml) and THF (14ml) was gently stirred with NaHCO₃ (0.84 g, 10 mmol) at 50-55° C. forthree days. The ligand loaded polystyrene beads (12B) were collected byfiltration and washed with water and MeOH. After being dried, the ligandcontaining beads (12B) were ready for analytical testing.

The composition (12B) prepared by this Example corresponds to Formula 7wherein SS is polystyrene, A and X are represented by the methylenegroup (Formula 10 where d is 1, c is 0 and e is 0), covalently bondingSS to the L(HOPO)₃ ligand which is the tris(HOPO)tetramine ligand ofExample 6.

The process of selectively and quantitatively concentrating and removinga desired ion or group of desired ions present at low concentrationsfrom a plurality of other undesired ions in a multiple ion sourcesolution in which the undesired ions may be present at much higherconcentrations comprises bringing the multiple ion containing sourcesolution into contact with a polyhydroxypyridinone-containingparticulate solid support material shown in Formula 7 which causes thedesired metal ion(s) to complex with the polyhydroxypyridinone portionof the composition and subsequently breaking or stripping the desiredion from the complex with a receiving solution which forms a strongercomplex with the desired ions than does the polyhydroxypyridinoneligand. The receiving or recovery solution contains only the desiredmetal ions in a concentrated form. Preferably the hydroxypyridinoneligand solid support composition will be contained in a column whereinthe source and receiving solutions can flow through by gravity. Ifdesired, the flow rate of these solutions can be increased by applyingpressure (with a pump) on the top of the column or by applying a vacuumin the receiving vessel.

The hydroxypyridinone-ligand solid support functions to attract thedesired metal cations according to Formula 11:

SS-A-X-L(HOPO)_(n)+DI→SS-A-X-L(HOPO)_(n):DI  Formula 11

Except for DI, Formula 8 is the same as Formula 7 wherein SS stands forsolid support, A is a covalent linkage mechanism, X is a hydrophilicspacer grouping, and L(HOPO)_(n) is a ligand comprising a ligand carrierL, n is an integer of 3 to 6 and L stands for apolyhydroxypyridinone-containing ligand. DI stands for desired ion beingremoved.

Once the desired metal ions are bound to thepolyhydroxypyridinone-containing ligand, they are subsequently separatedby use of a smaller volume of a receiving liquid according to Formula12:

 SS-A-X-L(HOPO)_(n):DI+receiving liquid→SS-A-X-L(HOPO)_(n)+receivingliquid:DI  Formula 12

The preferred embodiment disclosed herein involves carrying out theprocess by bringing a large volume of the source multiple ion solutioninto contact with a polyhydroxypyridinone ligand-solid supportcomposition of Formula 7 in a separation column through which themixture is first flowed to complex the desired metal ions (DI) with thepolyhydroxypyridinone ligand-solid support composition as indicated byFormula 11 above, followed by the flow through the column of a smallervolume of a receiving liquid, such as aqueous solutions of HBr, HCl,EDTA, NH₃, NaCl, NaI, HNO₃, H⁺ and others which either form a strongercomplex with the desired metal ion than does thehydroxypyridinone-containing ligand bound to the particulate solidsupport and/or have greater affinity for the bound ligand under theseconditions than does the desired ion. In this manner, the desired metalions are carried out of the column in a concentrated form in thereceiving solution. The degree or amount of concentration will obviouslydepend upon the concentration of desired metal ions in the sourcesolution and the volume of source solution to be treated. The specificreceiving liquid being utilized will also be a factor. Generallyspeaking, the concentration of desired transition, post-transition oractinide metal ions in the receiving liquid will be from 20 to 1,000,000times greater than in the source solution. Other equivalent apparatusmay be used instead of a column, e.g., a slurry which is filtered andthen washed with a receiving liquid to break the complex and recover thedesire metal ion(s). The concentrated desired metal ions are thenrecovered from the receiving phase by known procedures.

Illustrative of desired transition metal ions which have strongaffinities for polyhydroxypyridinone-containing ligands bound to solidsupports are Fe(III) from concentrated 1% to 5% HF and NH₃; Pu(IV),Th(IV), Zr(IV) and Hf(IV) from nitric acid solutions; Cu(II), Zn(II),Ni(II), Cd(II), Ni(II), Pb(II), Ag(I), Hg(II) from less acidic feedstreams; and 3+ actinides, lanthanides, Al(III), Ga(III) from slightlyacidic solutions. This listing of preferred cat ions is notcomprehensive and is intended only to show the types of preferred metalions which may be bound to polyhydroxypyridinone-containing ligandsattached to solid supports in the manner described above.

Removal of Desired Molecules With Cation-Ligand-Matrix Compositions

The following examples demonstrate how thepolyhydroxypyridinone-containing ligand bound to a solid supportcomposition of Formula 7 may be used to concentrate and remove desiredions. The polyhydroxypyridinone ligand-containing solid supportcomposition is placed in a column. An aqueous source solution containingthe desired metal ion or ions, in a mixture of other metal ions whichmay be in a much greater concentration, is passed through the column.The flow rate for the solution may be increased by applying pressurewith a pump on the top of the column or by applying a vacuum in thereceiving vessel. After the source solution has passed through thecolumn, a much smaller volume of a recovery solution, i.e., an aqueoussolution which has a stronger affinity for the desired metal ions thandoes the polyhydroxypyridinone-containing ligand, is passed through thecolumn. This receiving solution contains only the desired metal ions ina concentrate form for subsequent recovery. As noted above, suitablereceiving solutions can be selected from the group consisting of HBr,HI, HCl, NaI, NaCl, NaBr, Na₄EDTA, Na₃NTA, NH₃, NH₄OH, ethylenediamineand mixtures thereof. The preceding listing is exemplary and otherreceiving solutions may also be utilized, the only limitation beingtheir ability to function to remove the desired metal ions from thepolyhydroxypyridinone ligands.

The following examples of separations and recoveries of transition metalions by the inorganic support-bound hydroxypyridinone-containing ligandswhich were made as described in Examples 10 through 12 are given asillustrations. These examples are illustrative only, and are notcomprehensive of the many separations of metal ions that are possibleusing the materials of Formula 7.

Example 13

A 0.1 g column (6 mm diameter×8 mm height) of ligand-containing silicabeads from Example 10 was prepared. The column was cleaned with twoaliquots of 5 mll of 98% H₂SO₄ followed by two aliquots of 18.2 MΩ H₂Oat ˜0.1 ml/min. The column was then loaded with 20 ml of 0.05M Zr(IV) asthe NO₂ ⁻ salt in 5M HNO₃. The Zr was reduced from a 5 ppm feed inputlevel to a <1 ppm output level. The Zr removed by the column was thenquantitatively recovered (within analytical error) in 5 ml of 98% H₂SO₄eluant at a flowrate of ˜0.1 ml/min. The Zr analysis was performed usingInductively Coupled Plasma Spectroscopy (ICP).

Example 14

The procedure of Example 13 was repeated, using the ligand-containingacrylate beads of Example 11 in a 6 mm×12 mm column. The Zr was reducedfrom a 5 ppm level in the feed to a <1 ppm exiting level and the Zr wasquantitatively recovered in the 98% H₂SO₄ eluant.

Example 15

The procedure of Example 14 was repeated, using the ligand-containingacrylate beads of Example 11 in a 6 mm×12 mm column but with 10 ml ofFe(III) in 0.5% HF as the feed solution and using 37% HCl as thecleaning and elution solution. Graphite Furnace Atomic AbsorptionSpectroscopy was used for the analysis. The 1 ppm Fe in the feed wasreduced to <0.1 ppm Fe in the output and the Fe was quantitativelyrecovered (within analytical error) in the 37% HCl eluting solution.

From the foregoing, it will be appreciated that the inorganic solidsupport bound polyhydroxypyridinone-containing ligands of Formula 7 ofthe present invention provide a material useful for he separation andconcentration of the transition, post-transition and actinide metalcations from mixtures of those cations with other metal cations, H⁺ andsoluble complexes such as F⁻. The metal ions can then be recovered fromthe concentrated recovery solution by standard techniques known in theart. Similar examples have also been successfully established for manyother transition metal ions.

The variety of L(HOPO)_(n) ligands described by Formula 7 showsignificant improvement in interaction strength for several specificseparations such as Fe from HF. However, particular spacing of thehydroxypyridinone moieties aids in obtaining even greater interactionstrengths. For example, the ligands of Examples 6, 7, and 8 have greaterFe(III) binding strength under the same conditions than those ofExamples 5 and 9. Hence, optimal use of the invention in some cases alsoincludes particular spacings compared to others. Such may be readilydetermined through routine experimentation by one skilled in the art.Additionally, in a minority of cases, such as the complexing of very lowconcentrations of iron in the presence of high concentrations offluoride, not all 6 coordination sites may be involved in the complexingof iron. In cases such as this, for example, the iron may bind to only 4of the coordination sites leaving 2 fluorides bound. However, the ligandis still fully complexed with iron and fluoride and is functional forpurposes of the present invention.

Although the invention has been described and illustrated by referenceto certain specific solid support-bound polyhydroxypyridinone-containingligands of Formula 7 and processes of using them; analogs, as abovedefined, of these hydroxypyridinone-containing ligands are within thescope of the compositions and processes of the invention as defined inthe following claims.

What is claimed is:
 1. A method for concentrating, removing, and separating selected ions from a source solution comprising the steps of: (a) contacting said source solution having a first volume with a composition comprising a polyhydroxypyridinone-containing ligand covalently bonded to a particulate solid support through a hydrophilic spacer having the formula: SS-A-X-L(HOPO)_(n) where SS is a particulate solid support, A is a covalent linkage mechanism, X is a hydrophilic spacer grouping, L is a ligand carrier, HOPO is a hydroxypyridinone spaced on the ligand carrier to provide a minimum of six functional coordination metal binding sites, and n is an integer of 3 to 6 with the proviso that when SS is a particulate organic polymer, A-X may be combined as a single covalent linkage; wherein said L(HOPO)_(n) portion of the composition has an affinity for said selected ions such as to form a complex between said selected ions and said HOPO moieties of said composition; (b) removing the source solution from contact with said composition to which said selected ions have been complexed; and (c) contacting said composition having said selected ions complexed thereto with a smaller volume, compared to said first volume, of an aqueous receiving solution in which said selected ions are either soluble or which has greater affinity for such selected ions than does the ligand portion of the composition thereby quantitatively stripping such selected ions from the ligand and recovering said selected ions in concentrated form in said receiving solution.
 2. A method according to claim 1 wherein, in said composition, said ligand carrier L is configured such that there are at least two atoms on carrier L separating the attached HOPO groups to provide a stereoconfiguration to optimize the HOPO metal binding sites.
 3. A method according to claim 2 wherein, in said composition, HOPO is a member selected from the group consisting of 3-hydroxy-2(1H)-pyridinone, 1-hydroxy-2(1H)-pyridinone and 3-hydroxy-4(1H)-pyridinone covalently bonded to ligand carrier L through a functionality other than the hydroxy or carbonyl moieties on the pyridinone ring.
 4. A method according to claim 3 wherein, in said composition, SS is a inorganic solid support selected from the group consisting of sand, silica gel, glass, glass fibers, alumina, zirconia, titania, and nickel oxide and combinations thereof.
 5. A method according to claim 4 wherein, in said composition, A is a member selected from the group consisting of Si(Z,Z)-O, wherein Z independently represents members selected from the group consisting of Cl, Br, I, lower alkyl, lower alkoxy, substituted lower alkyl or substituted lower alkoxy and O-SS.
 6. A method according to claim 5 wherein, in said composition, X is a member represented by the formula: (CH₂)_(a)(OCH₂CHR¹CH₂)_(b) wherein R¹ is a member selected from the group consisting of H, SH, OH, lower alkyl, and aryl; a is an integer from 3 to 10; and b is an integer of 0 or
 1. 7. A method according to claim 3 wherein, in said composition, SS is a particulate polymeric organic solid support matrix selected from the group consisting of polyacrylate, polystyrene, and polyphenol and combinations thereof.
 8. A method according to claim 7 wherein, in said composition, A and X combined are represented by the formula: —(CH₂)_(x)—(Y)_(y)—(CH₂)_(z)— where y is an integer of 0 or 1; x and z are independently integers between 0 and 10; and Y is member selected from the group consisting of O, S, C═N, CO, CONH, CSNH, COO, CSO, NH, NR, SO, SO₂, SO₂NH, C₆H⁴ and CH₂C₆H₄ where R is lower alkyl with the proviso that at least one of x, y and z must be at least
 1. 9. A method according to claims 6 or 8 wherein, in said composition, L is a polyamine carrier.
 10. A method according to claim 9 wherein, in said composition, each HOPO group on the L carrier is separated by at least four non-hydrogen atoms.
 11. A method according to claim 10 wherein, in said composition, n is
 3. 12. A method according to claim 10 wherein, in said composition, n is
 4. 13. A method according to claim 8 wherein, in said composition, y is 1 and Y is CONH.
 14. A method according to claim 3 wherein said selected ion is a member selected from the group consisting of transition, post-transition, actinide and lanthanide metal ions.
 15. A method according to claim 14 wherein said selected ion is a member selected from the group consisting of transition metal ions, lanthanide series ions and actinide series ions.
 16. A method according to claim 14 wherein said selected ions are transition metal ions.
 17. A method according to claim 14 wherein said selected ions are lanthanide series ions.
 18. A method according to claim 14 wherein said selected ions are actinide series ions.
 19. A method according to claim 14 wherein said source solution is a nitric acid solution and said selected ions are members selected from the group consisting of Pu(IV), Th(IV), Zr(IV) and Hf(IV).
 20. A method according to claim 14 wherein said source solution is neutral to slightly acidic and said selected ions are members selected from the group consisting of Cu(II), Al(III), Ga(III), Ni(II), Zn(II), Cd(II), Pb(II), Ag(I), and Hg(II).
 21. A method according to claim 14 wherein said source solution is a 1 to 5% HF or NH₄F solution and said selected ion is Fe(III). 